Production of foam products from tall oil alkyds and a liquid diene polymer



States PRODUCTION OF FOAM PRODUCTS FROM TALL U.S. Cl. 2602.5 15 ClaimsABSTRACT OF THE DISCLOSURE The invention relates to a method of foaminga mixture of an alkyl of an insaturated fatty acid, sulfur monochlorideand a liquid diene polymer and the product obtained therefrom.

This invention is directed to novel foam products, both flexible andrigid, which are based on a tall oil derivative or alkyd as a reactivecomponent of the cell-forming system.

It has been a primary objective of this invention to produce foams whichwill contain large proportions of tall oil, in some instances as high as60% or more, and which will have sufficiently low densities and/or highstrengths to render them useful, for example, as packaging materials.

Tall oil is a by-product of the sulfate process for making pulp frompine. Although it is a variable mixture, illustratively about 90% of thecrude product is acidic materials usually comprising approximately equalparts of rosin acids and fatty acids. The remainder is a complex mixtureof fatty acid esters, sterols, higher alcohols, hydrocarbons anddecomposition products. The most important fatty acid constituents oftall oil are singly and doubly unsaturated fatty acids such as oleic andlinoleic acids. Abietic acid and its derivatives are the major rosinacids in crude tall oil.

In the pulping process the fatty acids and rosin acids present in wooddissolve in the liquor as sodium soaps. These soaps or crude tall oilskimmings rise to the surface of the black liquor as the total solidscontent is increased and as the liquor starts to cool. Addition of amineral acid such as sulfuric acid forms the mixture of rosin and fattyacids which constitutes the crude tall oil of commerce.

There are also available various refined or purified grades of tall oil.Some of these consist largely of the fatty acid components of crude talloil in which the rosin acid content has been reduced or almostcompletely removed, and such high fatty acid purified forms of tall oilare also contemplated for use herein.

In the production of foams according to the present ir1- vention, thetall oil starting material is first converted to a higher molecularweight alkyd intermediate, by reaction with a polyhydric alcohol and acarboxylic acid having at least two acidic groups in the molecule.

Broadly put, the foam is produced from a tall oil alkyd by reacting thealkyd with a diene polymer, as hereinafter identified, and sulfurmonochloride. The precise nature of the interaction between thesecomponents in the practice of this invention is not presently known, butwe believe that the sulfur monochloride forms an S- or -SS bond whichcross-links polymer chains formed from the diene polymer and/ or thealkyd. The sulfur monochloride also produces gaseous reaction productswhich contribute to the flow or generation of the foam. The reaction ispreferably but not necessarily carried out in the presence of avolatilizing, non-reactive organic solvent.

atent 3,444,105 Patented May 13, 1969 The diene polymers chemicallyincorporated in the foam with the alkyd and sulfur monochloride aresynthetic, low molecular weight polymers of butadiene, and includehomopolymers and copolymers of butadiene and alkyl, aryl and substitutedderivatives thereof. We prefer to use unsaturated liquid diene polymershaving molecular weights in the range of roughly about 500 to 10,000.Polymers we have found to be particularly useful for this purposeinclude butadiene homopolymers and copolymers with styrene,butadiene-acrylic acid copolymers, butadiene-methacrylic acidcopolymers, and butadiene-acrylonitrile copolymers, and mixturesthereof.

Sulfur monochloride, incorporated into the foam with the alkyd and thediene polymer, is conventionally represented by the formula S Cl and isa highly reactive fuming liquid having a specific gravity of 1.69 atroom temperature.

This invention is predicated in part upon the discovery of a reactionsystem wherein the intense reactivity of S CI can be controlled topermit useful foam products to be obtained.

The present foams are preferably produced from a mixture in the liquidstate which comprises, for each parts of tall oil alkyd, 5-110 partsdiene polymer and l0- parts of sulfur monochloride. It is especiallyadvantageous to react a mixture of approximately equal parts of dienepolymer and tall oil alkyd together with 40-90 parts S Cl based on 100parts of the mixture, i.e., 100 parts total of the diene and alkyd. Bothflexible and rigid foams can be produced, depending upon the proportionsof ingredients and the reaction conditions.

Examples of commercially available liquid diene polymers which we havefound to be suitable for interaction with tall oil alkyd and sulfurmonochloride to produce foams include:

Buton 100, a liquid copolymer of butadiene and styrene in 34:1 weightratio comprising about 65% 1, 2 adduct and 35% 1, 4 adduct, having amolecular weight of about 2,0002,600, an iodine number of about 275 to330-, and viscosity of 3,500 poises, produced by Enjay Corporation;

Buton 150, a liquid butadiene homopolymer having a molecular weight ofabout 2,50-03,500, an iodine number of about 410, comprising 65% 1, 2adduct and 35% 1, 4 adduct, produced by Enjay Corporation;

Butarez CTL, Type II, an acid-terminated liquid copolymer of butadieneand acrylic acid having a carboxy content of 1.66%, and a molecularweight of 5500, produced by Phillips Petroleum;

BD, a liquid homopolymer of butadiene, produced by Sinclair Refining.

We have also found it possible to produce foams from tall oil alkyd andsulfur monochloride alone, without the inclusion of a diene polymer.However, such foams are in general relatively heavy compared with foamscontaining the diene polymer and are poorer in compressive strength.

As suggested, the reaction of the foam components is advantageouslycarried out in the presence of an organic solvent for the diene polymer,such as a Freon, pentane or naphtha. While the boiling range of thesolvent is not critical, a solvent having a boiling point in the rangeof about 20 to 40 C. is especially useful.

In the preliminary alkydization of crude or refined tall oil, the oil isfirst esterified with a polyol such as glycerine and is then reactedwith an organic acid or acid anhydride such as maleic anhydride. In thisreaction heat is applied and a catalyst may be used to cause a highermolecular weight product to be formed as water is split off.

Among the polyols which are suitable for the production of tall oilalkyds there may be specifically mentioned ethylene glycol, propyleneglycol, glycerine, trimethylol 3 4- ethane, trimethylol propane,pentaerythritol, diand trian acid number of about 5 to 50 is obtainedand viscosity pentaerthritol, and hydrogenated bisphenol A. is in therange of Z4 to Z8 as measured by the Gardner Among the suitable acidsand acid anhydrides are method. phthalic anhydride, isophthalic acid,rnaleic anhydride, Example G of the Table I illustrates the productionfumaric acid, and adipic acid, all of which are characterof an alkydusing tall oil fatty acids, in the absence of ized by an ability toenter into dicarboxylic reactions. The 5 the rosin component of talloil. It will be appreciated specific acids and alcohols as listed are ofcourse only rethat other sources of unsaturated fatty acids having 11presentative, and the production of tall oil alkyds suitable to 22carbon atoms in the molecule can be used in the for use as startingmaterials in the production of foams is alkyd production.

not limited to the use of these materials. The production of an alkydwhich includes a diene In the production of the alkyd the proportions oftall polymer as a constituent thereof, in addition to the polyol oil,polyol, and polycarboxylic acid may vary rather and carboxylic acids, isshown in Examples I and J of widely. The alkyds on which the foams ofthis inven- Table I.

tion are based are preferably produced by the reaction, It iscontemplated that the molecular weight of the with each 100 parts talloil or tall oil fatty acids, of 3-30 15 alkyd can be increased prior tofoaming by bodying it parts of a polyol and 3-25 parts of a dicarboxylicacid with a small proportion of S Cl insufficient in amount or acidanhydride. We have found that the polyol to be to cause foaming, forexample 1 to 10 parts per hundred used should preferably have three ormore hydroxyl groups parts alkyd.

in the molecule although diols may be used in mixture In the productionof the foam from the alkyd we therewith, as will be seen. prefer thatall of the ingredients except the sulfur mono- In addition to thesecomponents, a catalyst such as chloride be premixed and that the sulfurmonochloride lithium hydroxide may be used, preferably in the proporbeadded last. Upon blending the sulfur monochloride tions of about 0-1part to each 100 parts by weight of tall into the mixture, foam quicklystarts to rise, often in a oil. The mixture may also include anadditional to 125 minute or less.

parts of a diene polymer which may be the same type of 25 The foam willset or cure without the application of diene polymer as is subsequentlyto be incorporated in external heat. Optimum sulfur monochloride contentfor the reaction of the alkyd to produce the foam. given alkyds anddiene contents can be determined by For purposes of illustration of thetypes of alkyds which making a series of tests with compositions havingdifcan be used, the production of several suitable alkyds from ferent SCl contents, the proportions of other ingredients tall oil, a polyol,and a polycarboxylic acid or anhydride remaining the Same.

is illustrated in Table -I. All alkyd formulae set forth here- Theproduction of a foam from an alkyd of the type inafter are based upon100 parts of the tall oil, either of described can best be seen fromExample 1 following,

the crude or refined type, and all quantities are part by whichpresently constitutes our preferred formulation for weight per 100 partstall oil unless otherwise noted. a flexibl fo m;

TABLE I.PRODUOTION OF ALKYD Example A B 0 Tall oil: Type, gms Crude,100.0 Crude, 100.0 Refined, 100.0.

Polyol: Type, gms G1ycerme,15.1 Glycerine,15.1 Glycerine, 15.6.

Acid: Type, gins Maleic nhydrldc, 7.4.. Maleic anhydrlde,7.4 Maleicanhydride, 7.6.

Catalyst: Type, grns.. L1OH.Hz0, 0.1

Reaction conditions Tall oil, polyol, catalyst heated 4 hrs. Tall oil,polyol heated 4 hrs. at 260 C. Talloll,polyol heated2.5 hrs. at 265 C.at 235 0. peak temp; acid added peak temp; acid added, heated 9 peaktemp; acid added, heated 5.5 aggpheated 8 hrs. at 260 0. peak hrs. at260 0. peak temp. hrs. at 275 0. peak temp.

Example D E F Tall oil: Type, gms Crude, 100.0 Crude, 100.0 Crude,100.0.

Polyol: Type, gm Trimethylol propane, 28.5 Acid: Type, gms. Adlpic,21.5; maleic anhydr Catalyst: Type, gms..

Trimethylol propane 28.5.

Adipicacld,21.5.

Glycerine, 18.0. Phthalic anhydride, 15.9.

Reaction conditions Tall oil. polyol, adipic acid heated Tall oil,polyol nd eated 7.8 Tall oil and polyol heated 1.5 hrs. at hrs. at 2660. peak temp; maleic hrs. at 280 0. peak temp. 270 C. Phthalie added andheated auhydride added, heated 1 hr. at over 9.1 hrs. at 250 0. peaktemp. 280 0. peak temp.

Example G H Tall oil: Type, gms Mixed fatty acids, 100.0 Crude, 100.0.

Polyol: Type, gms.. Glyccrine, 18.4 Ethylene glycol, 7.6;pentaerythritol, 8.8.

Acid: Type, gms Maleic anhydride, 4.5; phthalic anhydride, 6.6.. Maleicanhydride, 7.4.

Tall oil wtJpolyol wt Polyol wt./acid wt Reaction conditions Fattyacids, polyolheeted 3 hrs. at 250 C. peak temp, Tall oil, polyols heated7.5 hrs. at 210 0. peak temp;

acids added, heated 11 hrs. at 240 0. peak temp. acid added, heated 10hrs. at 269 0. peak temp.

Example I J Tall oil: Type, gms.-- Crude, 100 0 Refined, 100.0.

Diene polymer: Type Hilton 150, 10 Buton 100, 50.0.

Polyol: Type, gms Pentaerythritol Pentaerythntol, 5.0.

Acid: Type, gms Maleic anhydride, 5.0 Maleic anhydride, 5.0.

Reaction conditions Tall oil, polymer heated .5 hr. to 260 0.; acidadded, Tall oil, polymer heated 1 hr. to 260 0.; acid added, heated .08hr. at 250 0.; polyol added, heated .12 heated .08hr. at 270 0.; polyoladded, heated .12 hr. hr. at 250 0. at 250 0.

As shown in the table, the tall oil and polyol can ad- Example 1vantageously first be mixed and heated to a temperature P a a1 ts by inthe range of about 210-280 C. over a period of about Weight 0.5 to 10hours. The acid or acid anhydride can then be Alkyd produced accordingto Example A of added and the mixture again heated, to a temperature 1n7 Table I 10M) the range of about 220 to 290 C. for 1 to 15 hours. ButonThese conditions and temperatures are to be considered p q illustrativeonly and should not be taken as limiting the Pentane types of alkydswhich can be used. Dow-Corning 232 Surfactant We prefer to continue theheating of the alkyd until S Cl All the components except the S Cl werefirst mixed for useful proportions of the surfacant are about 0.5 to 5about a minute in a counter-rotating mixer. Mixing the parts per 100parts alkyd. other components prior to the addition of S Cl enables Apulverized alkali metal carbonate or bicarbonate may better homogeneityto be achieved, because foaming bebe added as a secondary blowing agent,and provides adgins quickly upon addition of the S 01 After mixing in 5ditional control of foam density. The most useful proporthe S Cl themixture is permitted to set up in a mold of tions are 0.5 to 5 parts per100 parts alkyd. These matedesired shape. rials decompose to evolve COduring the reaction, and

Foam generation or blowing with this formulation beit is believed thatthe alkali reacts with HCl evolved from gins quite rapidly, typicallywithin a few seconds after the reaction of the S Cl to form thecorresponding chloaddition of the S Cl and the reaction mass rises inthe ride salt. Since this reduces the acidity of the foam, it is mold asfoaming occurs. Mixing may be terminated once especially useful if theproportion of carbonate or bicarvisible foaming begins in order tominimize density. bonate is in substantial stoichiometric balance withthe Other examples of the production of foams from alkyds quantity ofHCl produced by the S Cl which is to be of this type are shown inExamples 2 through 12 of Table incorporated in a given formulation.

II. All formulae set forth in the table are based upon The prop rt n Of2 2 to achieve the desired degree 100 parts of the alkyd, and allquantities are parts by of foaming and product rigidity or flexibilitycan readily weight per 100 parts alkyd unless otherwise noted. bedetermined for a specific polymer and/or alkyd from TABLE II.PRODUCTIONOF FOAM Example Number 2 3 4 5 6 7 Alkyd, gms 100.0 100.0 100.0 100.01Q0.0.. 100.0.

Diene polymer: Type, gms"-.. Buton 100, 100.0 Buton 100, 100.0 Buton100, 100.0. Buton 150, 100.0. Sinclair BD, 100.0.-. Butarez CTL,II,100.0. S2012, gms 45.3 84.7 .a 146.0 84.7 84.7 84.7.

Freon-11. gms Solvent: Type, gms Na SlOa, gms NaHC 03, gms Surfactant:Type, gms

Example Number 8 9 10 11 12 Alkyd, gms Diene polymer: Type, gms...SzClz, gms Freon-11, gms

100.0 100.0 100.0 100.0 100.0. Buton 100, 32.4..-- Buton 100, 13.3.-..Buton 100, 13.3.... Buton 100, 6.7..." Buton 100, 6.7. 55.9 28.4 42.317.0 67.7.

10.0. Pentane, 16.7. 0.7.

Surfactant: Type, gms DC-232, 0.7.

The use of a volatilizing solvent such as pentane rea series of testcompositions in which the other ingrediduces the viscosity of the dienepolymer and permits it to ents are held constant while the proportionsof S Cl are be mixed more readily with the alkyd to achieve morechanged.

uniform reaction. While the reaction can be conducted in In each of theexamples of Table II the sulfur monothe absence of a solvent, as will beseen hereinafter, their chloride was the last ingredient to be added. Inthose use is preferred. formulations containing Freon-11 we found itadvanta- One or more other propellants or solvents for the diene geousto blend in the Freon immediately prior to adding polymer such asFreon-11 (CCI F, boiling point about the sulfur monochloride in order tominimize volatiliza- 24 C.) or naphtha may be used in place of some orall tion. Generally speaking, generation of the foam should of thepentane (boiling point about 36 C.). Solvents of proceed roughly apaceof the curing reaction so that the higher boiling point such as VM & Pnaphtha (boiling 4,5 foam will be relatively stable as it is generatedand will point 93149 C.) have a generally opposite effect, probe setbefore it might collapse. Where a large volume of viding longer workingperiods before the start of the rise, foam is to be produced in a singlebatch, it may be debut total rise is reduced. In general, any solventfor the sirable to apply cooling means to prevent reaction temdienepolymer or S C1 may be used which is not disperature from becomingexcessive. The product will selfadvantageously reactive with thecomponents, but we harden without further treatment, usually after twoor prefer aromatic or aliphatic solvents which are completely threehours. The mixture may be applied to a mold or inert toward S Cl Thegenerally useful total proportions container from a foaming gun whereinan S Cl stream of solvents such as pentane and Freon-l1 are about 10 tois contacted in a mixing head at a controlled rate with a 60 parts per100 parts alkyd, though it will be appreciated stream containing theother ingredients and the mixed that certain polymers will be moresoluble in given solstreams are fed continuously into a mold or onto amovvents than others and that the proportions can be varied ing belt.accordingly. The density of a given foam composition will depend Thesodium silicate employed may for example be a upon conditions of mixing,foam volume, the manner in Ballm aqueous Solution, Containing about 11%2 which the monochloride is added, the absence or presence 2 y Weight ehave found it to be SIJT- and quantity of rosin, the quantity of blowingagents or P Y effeetive'il} eontfilllltlng to a finer e Florevolatilizing solvents, and other factors. Diene polymers "Inform Cellformatlon' Whlle the use of Na2s103 15 not of lower unsaturation thanthe butadiene homopolymers,

gecezsary m the .3 a a g f g such as butadiene-styrene copolymers havinga butadiene/ l S a same we consl er It to e eslra 6 most styrene weightratio of less than 1.0 are believed to give ful range of addition of the47 sodium silicate solution 5 is about 05 to 2.0 parts Per 100 partsalkyd. more easily controllable foams and foams with lower Thesurfactant DC 232 is a dimethyl polysiloxane densmes' produced by DowCorning Corporation. It has the effect general the propoftlon of sulfurmonociflonde to of making the cells of the foam finer and causes ahigher be mcoltpofated Should ll'lcfease as he alkyd/dlene polyfoamrise, i.e., it reduces foam density. The use of this mar rat) Increasesto glve the Same degree of ngldltyor another comparable surfactant istherefore desirable, AS prevlously Suggested, We have also found itPossible although not absolutely necessary. Other representative toProduce foams y the dlfeet reaction of a tall Oil alkyd surfacants whichare suitable for use include those listed with Sulfur monochloridealone, that Withellt the in our copending application Ser. No. 455,596,filed May corporation of a diene polymer. The production of sev- 13,1965 to which reference is hereby made. The most eral such foams fromalkyd of the type previously described is shown in Table In. Productionof these foams proceeds in the manner described previously, except thatno diene is added.

8 saturated fatty acid having 11 to 22 carbon atoms, and about 100 partsof an unsaturated liquid polymer of butadiene having a molecular weightin the range of TABLE III Example Number 13 14 15 16 17 Alkyd: Ex.No.,gms F, 1000 G, 100.0 H, 100.0 A, 100.0 A, 100.0. S1011, gms 22.822.8 24.8 24.8 37.2.

Freon-11, gms Solvent: Type, gms

In the foregoing examples the crude tall oil used had a fatty acidcontent of about 40 to 55%, a rosin acid content of 36-46%, and 53-10%unsaponifiables. Its acid number was about 160-170, its saponificationnumber was 165-175, and its iodine value was 140-150.

The alkyd and/ or diene polymer or a mixture thereof can be bodied topartially increase its molecular weight in advance of the foam producingreaction, by pre-reaction with a proportion of sulfur monochloride whichis insufiicient to cause foaming or gellation. To carry out theprebodying reaction effectively it is important that the proportion of SCl which is added be such as to cause the liquid to thicken withoutfrothing, charring or gellation, which would render further reactionineffective or inoperative or which would harm foam quality.

The foam products produced in accordance with this invention are adaptedto be used for packaging, insulation purposes, and as core materials insandwich or laminated products.

While we have described the preferred embodiment of our invention, thoseskilled in the art will recognize that the invention is susceptible tovarious modifications and variations within the scope of the followingclaims.

What is claimed is:

1. The method of producing a foam which comprises mixing together andspontaneously interreacting an alkyd of an unsaturated fatty acid having11 to 22 carbon atoms, sulfur monochloride, and a liquid diene polymerselected from the class consisting of butadiene homoploymers,butadiene-styrene copolymers, butadiene-acrylic acid copolymers,butadiene-methacrylic acid copolymers and butadiene acrylonitrilecopolymers, and mixtures thereof, the proportions in the mixture beingsuch that diene polymer is present in the amount of about to 110 partsto each 100 parts of the alkyd and further such that the S Cl is presentin the range of about to 150 parts to each 100 parts of the alkyd, andpermitting the foam to expand and self-cure.

2. The method of claim 1 wherein said alkyd is produced by the reactionof tall oil with a polyol and a dicarboxylic acid.

3. The method of claim 2 wherein said polyol has three reactive hydroxylgroups per molecule.

4. The method of claim 3 wherein said alkyd is produced by the reactionof tall oil with glycerin and maleic anhydride in approximate 100/ /7weight ratio.

5. The method of claim 1 wherein said diene polymer is present in aboutequal proportion to said alkyd.

6. The method of claim 5 wherein said sulfur monochloride is present inthe amount of about 40-90 parts per 100 parts total of said diene andsaid alkyd.

7. The product of the process of claim '1.

8. The method of producing a foam which comprises, preparing a mixturehaving as the polymerizing components thereof about 100 parts of analkyd of an un- 15 SOD-10,000, in the presence of a solvent for saidpolymer having a boiling point in the range of -40 C., mixing therewitha proportion of S Cl sufficient to cause foaming, and permitting theresulting foam to expand and self-cure.

20 9. The method of claim 8 wherein said mixture also contains Na SiO asa cell control agent.

10. The method of claim 8 wherein said mixture also contains a CO-generating salt of an alkali metal.

11. The method of claim 8 wherein said alkyd has 25 been previouslyreacted with S Cl in amount sufiicient to thicken said alkyd andincrease its molecular weight but not to cause frothing thereof.

12. The method of producing a foam which comprises mixing together andspontaneously interreacting an alkyd of an unsaturated fatty acid having11 to 22 carbon atoms with sulfur monochloride in proportions of 100parts alkyd to 10-50 parts of said monochloride, and permitting the foamto expand and self-cure.

13. The method of claim 12 wherein said alkyd is the 3 product of thereaction of tall oil with a polyol and a dicarboxylic acid.

14. The method of producing a foam which comprises, reacting tall oil to:form an alkyd thereof with at least one polyol selected from the classconsisting of glycerine, pentaerythritol, propylene glycol, andtri-methylol propane, and with an acidic material selected from theclass consisting of maleic anhydride, phthalic anhydride, and adipicacid, in proportions equal to about 100 weight parts tall oil to 3-30parts polyol and 3-25 parts acidic material, preparing a mixture havingas polymerizable components thereof about 100 parts of said alkyd andabout 5-110 parts of an unsaturated liquid polymer of butadiene having amolecular weight in the range of about SOD-10,000, said mixture alsocontaining a volatilizable solvent for said polymer, mixing therewith aproportion of S CI sufficient to cause said mixture to foam, andpermitting the resulting foam to expand and self-cure.

15. The method of claim '14 wherein said alkyd also contains a butadienepolymer chemically combined therein with said polyol and acid.

References Cited UNITED STATES PATENTS 2,208,305 7/ 1940 Kittredge.2,234,545 3/1941 Auer 260-777 2,662,862 12/ 1953 Crouch. 2,888,417 5/1959 Crouch. 3,260,688 7/1966 Watanabe et al.

GEORGE F. LESMES, Primary Examiner.

MORTON FOELAK, Assistant Examiner.

U.S. Cl. X.R.

